A petrogenetic grid for pelitic schists in the system SiO2-Al2O3-FeO-MgO-K2O-H2O

A quantitative petrogenetic grid for pelitic schists in the system KFMASH that includes the phases garnet, chlorite, biotite, chloritoid, cordierite, staurolite, talc, kyanite, andalusite, sillimanite, and pyrophyllite (with quartz, H₂O and muscovite or K-feldspar in excess) is presented. The grid is based on thermodynamic data of Berman et al. (1985) and Berman (1988) for endmember KFASH and KMASH equilibria and natural Fe-Mg partitioning for the KFMASH system. Calculation of P-T slopes and the change in Fe/(Fe+Mg) along reactions in the KFMASH system were made using the Gibbs method. In addition, the effect on the grid of MnO and CaO is evaluated quantitatively. The resulting grid is consistent with typical Buchan and Barrovian parageneses at medium to high grades. At low grades, the grid predicts an extensive stability field for the paragenesis chloritoid+biotite which arises because of the unusual facing of the reaction chloritoid+biotite + quartz+H₂O = garnet+chlorite+muscovite, which proceeds to the right with increasing T in the KFMASH system. However, the reaction proceeds to the left with increasing T in the MnKFASH system so the assemblage chloritoid + biotite is restricted to bulk compositions with high Fe/(Fe+Mg+Mn). Typical metapelites will therefore contain garnet+chlorite at low grades rather than chloritoid + biotite.     

Experimental study of chloritoid stability at high pressure and various fO2 conditions

The reaction chloritoid (ctd)=almandine (alm)+diaspore+H₂O (CAD) has been reversed using Fe³⁺-free synthetic chloritoid and almandine, under fO₂ conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO₂ conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO₂ conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH₂O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H₂O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H₂O bracketed on the Fe/FeO buffer and under unbuffered fO₂ conditions. For fO₂ buffered by the assemblage Fe/FeO, aH₂O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO₂ buffered by the assemblage Ni/NiO, aH₂O=1. The aH₂O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H₂O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H ^o f,ctd and S ^octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and K_D=(Fe³⁺/Al)ctd/(Fe³⁺/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe³⁺ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl₂SiO₅(OH)₂ formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe³⁺ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H₂O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for K_D=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the K_D values reported from chloritoid+garnet+quartz+kyanite natural assemblages.     

Phase equilibria among pumpellyite,lawsonite, epidote and associated minerals in low grade metamorphic rocks

Phase relations of pumpellyite, epidote, lawsonite, CaCO₃, paragonite, actinolite, crossite and iron oxide are analysed on an Al-Ca-Fe³⁺ diagram in which all minerals are projected from quartz, albite or Jadeite, chlorite and fluid. Fe²⁺ and Mg are treated as a single component because variation in Fe²⁺/Mg has little effect on the stability of phases on the diagram. Comparison of assemblages in the Franciscan, Shuksan, Sanbagawa, New Caledonia, Southern Italian, and Otago metamorphic terranes reveals several reactions, useful for construction of a petrogenetic grid:

1. lawsonite+crossite + paragonite = epidote+chlorite + albite + quartz + H₂O
2. lawsonite + crossite = pumpellyite + epidote + chlorite + albite+ quartz + H₂O
3. crossite + pumpellyite + quartz = epidote + actinolite + albite + chlorite + H₂O
4. crossite + epidote + quartz = actinolite + hematite + albite + chlorite + H₂O
5. calcite + epidote + chlorite + quartz = pumpellyite + actinolite + H₂O + CO₂
6. pumpellyite + chlorite + quartz = epidote + actinolite + H₂O

     

Chloritoid-bearing metapelites associated with glaucophane rocks in western Crete,Greece

In western Crete, Greece, a widespread occurrence of chloritoid-bearing metapelites with the main mineral assemblage chloritoid-phengitic white mica-Fe-rich chlorite-quartz was recorded to form the country rock of glaucophane-bearing metabasalts. Six bulk rock analyses of the metapelites conform to the compositional restrictions evaluated by Hoschek (1967) for the formation of chloritoid. Three microprobe analyses revealed chloritoid compositions low in Mg and Mn, and, consequently, high in Fe. The metamorphic grade documented in the metapelites is obviously related to a subsequent prograde metamorphism by which, in the adjacent meta-basalts, epidote is formed at the expense of lawsonite. No relict of a high-P, low-T assemblage, in part well preserved in the meta-basalts, was recognized in the chloritoid schists. The significance of the metamorphic history is briefly discussed.     

Das P{\text{ - }}T{\text{ - }}X_{{\text{CO}}_{\text{2}} } Stabilitätsfeld von Lawsonit

At pressures which are expected in the earth's crust, the high temperature border of the lawsonite stability field is marked by reaction lawsonite = zoisite + kyanite/andalusite + pyrophyllite + H₂O. (1a) The equilibrium data of reaction (1a) have been experimentally determined, and the equilibrium curve is characterized by the following P, T-data: 4 kb; 360±20° C; 5 kb; 375 ±20° C; 7kb;410±20° C. In the P, T diagram the equilibrium curve of reaction lawsonite + quartz = zoisite + pyrophyllite + H₂O (6) is very close to the curve of reaction (1a); the distance is smaller than the error stated for curve (1a), i.e. below ±20° C. The stability fields of lawsonite and anorthite + H₂O are not adjacent fields in the P, T diagram. This means that no stable reaction of lawsonite to anorthite + H₂O can exist. Thus, the CaAl-silicate formed by the decomposition of lawsonite is always zoisite. Further, as shown by experimental determination of reaction calcite + pyrophyllite + H₂O = lawsonite + quartz + CO₂, (7) lawsonite can coexist with a gas phase only if the CO₂ content of the gas phase does not exceed 3±2 Mol-%. This means, for metamorphism of lawsonite glaucophane rocks, that the fluid phase that was present during metamorphism has been quite rich in H₂O. Ernst (1971, in press) who applied a different, indirect investigation method when studying the composition of the fluid-attending Franciscan and Sanbagawa metamorphism has come to the result that during metamorphism of lawsonite-glaucophane rocks the fluid phase did not contain more than 1–3 Mol-% of CO₂.     

Mineralogy of New Caledonian metamorphic rocks

Variations in chemistry and related physical properties of sheet silicates in the Ouégoa district with metamorphic grade are investigated. Weakly metamorphosed rocks prior to the crystallization of lawsonite contain phengite (d ₀₀₆=3.317–3.323 Å), chlorite and occasionally paragonite while interstratified basaltic sills contain chlorite, minor phengite and stilpnomelane. Pyrophyllite crystallizes before lawsonite in some metamorphosed acid tuffs and is also stable in the lawsonite zone. Paragonite, phengite and chlorite appear to be stable through the sequence from weakly metamorphosed rocks into high-grade “eclogitic” schists and gneisses. Optical, chemical and some X-ray diffraction data is given for representative sheet silicates. Electron probe analyses of 55 phengites, 21 paragonites, 57 chlorites, 12 vermiculites, 2 stilpnomelanes, and 2 chloritoids are presented in graphical form. All K-micas analysed are consistently phengitic (3.29–3.55 Si^iv ions per formula unit) and show limited solid solution with paragonite (4 to 13% Pa). The K∶Na ratio of the phengite is strongly dependant on the assemblage in which it occurs; the amount of phengite component and its Fe∶Mg ratio depends on bulk-rock composition. Phengites from acid volcanics have the highest Fe∶Mg ratio, highest phengite component and β refractive indices. Phengites from basic volcanics and metasediments of the epidote zone have the lowest Fe∶Mg ratio. Phengites from lawsonite-zone metasediments have intermediate Fe∶Mg ratios. The phengites show a small decrease in phengite component with increasing metamorphic grade. d ₀₀₆ for phengites varied from 3.302 to 3.323 Å but at least in the lawsonite and epidote zones appears to reflect composition and had little systematic variation with metamorphic grade; phengites from very low-grade rocks showed the longest values of d ₀₀₆. Paragonite shows almost no phengite-type substitution and only limited solid solution (4–12%) with muscovite. All paragonites (6) and most phengites (20) which have been examined are 2M₁ polymorphs; one Fe²⁺-phengite appears to be a 1M polymorph. The chemistry of chlorites closely reflects parent-rock chemistry. Chlorites from metasediments have distinctly higher Fe/(Fe+Mg) ratios than chlorites from basic igneous rocks; chlorites from the lawsonite and lawsonite-epidote transitional zone metasediments have the highest Fe/(Fe+Mg) ratios. In metabasalts Fe/(Fe+Mg) ratios appear to reflect individual variations in bulk-rock chemistry and show no direct correlation with metamorphic grade. There is little difference in Al/(Si+Al) ratio between chlorites from sediments and basic igneous rocks although in both lithologies the chlorites from the epidote zone appear to be slightly more aluminous. Fe-rich chlorites of the lawsonite zone metasediments have been altered by a process involving leaching of Fe and Mg and introduction of alkalies to a brown pleochroic Fe-vermiculite. Chemical and physical data for this vermiculite are given. The decrease in Fe/(Fe+Mg) ratio in chlorites and phengites on passing from the lawsonite to the epidote zone can be correlated with the crystallization of Fe-rich epidote and almandine in the epidote zone. Elemental partitioning between coexisting minerals has shown Ti to be partitioned into phengite, while Fe and Mn are strongly partitioned into chlorite. When either stilpnomelane or chloritoid coexists with phengite or chlorite, Fe and Mn are slightly enriched in the stilpnomelane or chloritoid relative to the chlorite.     

Phase relations in the greenschist-blueschist-amphibolite-eclogite facies in the system Na2O-CaO-FeO-MgO-Al2O3-SiO2-H2O (NCFMASH), with application to metamorphic rocks from Samos, Greece

Calculated phase equilibria among the minerals sodic amphibole, calcic amphibole, garnet, chloritoid, talc, chlorite, paragonite, margarite, omphacite, plagioclase, carpholite, zoisite/clinozoisite, lawsonite, pyrophyllite, kyanite, sillimanite, quartz and H₂O are presented for the model system Na₂O-CaO-FeO-MgO-Al₂O₃-SiO₂-H₂O (NCFMASH), which is relevant for many greenschist, blueschist, amphibolite and eclogite facies rocks. Using the activity-composition relationships for multicomponent amphiboles constrained by Will and Powell (1992), equilibria containing coexisting calcic and sodic amphiboles could be determined. The blueschist–greenschist transition reaction in the NCFMASH system, for example, is defined by the univariant reaction sodic amphibole + zoisite = calcic amphibole + chlorite + paragonite + plagioclase (+ quartz + H₂O) occurring between approximately 420 and 450 °C at 9.5 to 10 kbar. The calculated petrogenetic grid is a valuable tool for reconstructing the PT-evolution of metabasic rocks. This is shown for rocks from the island of Samos, Greece. On the basis of mineral and whole rock analyses, PT-pseudosections were calculated and, together with the observed mineral assemblages and reaction textures, are used to reconstruct PT-paths. For rocks from northern Samos, pseudomorphs after lawsonite preserved in garnet, the assemblage sodic amphibole-garnet-paragonite-chlorite-zoisite-quartz and the retrograde appearance of albitic plagioclase and the formation of calcic amphibole around sodic amphibole constrain a clockwise PT-path that reaches its thermal maximum at some 520 °C and 19 kbar. The derived PT-trajectory indicates cooling during exhumation of the rocks and is similar to paths for rocks from the western part of the Attic-Cycladic crystalline complex. Rocks from eastern Samos indicate lower pressures and are probably related to high-pressure rocks from the Menderes Massif in western Turkey. Received: 8 July 1997 / Accepted: 11 February 1998     

Staurolite-quartzite bands in kyanite quartzite at big rock,Rio Arriba County,New Mexico

Concordant igneous-looking bands of ferruginous bulk composition occur in a highly aluminous Precambrian metasedimentary series composed predominantly of kyanite quartzite. The bands consist of quartz, staurolite, and magnetite (partially martitized) with accessory amounts of muscovite, chlorite (pseudomorphous after biotite), chloritoid, apatite, and monazite. Quartz is found in three types (I–III) differing in appearance as well as in origin. Staurolite, in combination with quartz-II, shows peculiar radial sieve textures caused by mimetic crystallization after preexisting chloritoid rosettes. The chloritoid has been largely consumed, either by a reaction with hypothetical former kyanite to produce staurolite+ quartz with rock composition unchanged, or, possibly, by metasomatic introduction of oxygen (oxidation) to yield staurolite+quartz+magnetite; the remaining chloritoid, however, persisted in stable equilibrium with the other minerals of the rock. The staurolite quartzites are thus considered to represent original sedimentary bands which have undergone several stages of recrystallisation and (possibly) metasomatic modification during their metamorphic history. Their igneous aspect results from annealing crystallisation during a late static, i.e. postdeformational, thermal event of regional metamorphism.Chemical analysis of the staurolite shows no unusual features. For all staurolites plotted there is a positive relationship of the excess H⁺ over 2.0 and the Si⁺⁴-deficiency in the unit cell. This suggests partial substitution of 4 H⁺ for Si⁺⁴.The formation of staurolite in regional metamorphic rocks with excess silica, low alkali contents, and (FeO+MgO)/Al₂O₃ ratios < 1 showing chloritoid at lower grades appears to be governed, in many cases, by the reaction chloritoid+Al-silicate=staurolite+quartz+H₂O.The assemblage chloritoid-staurolite may be stable in regional metamorphism over a limited pressure-temperature range.     

Coexisting cummingtonite and calcic amphibole in amphibolites from the Schneeberg complex,Tyrol, Austria

Summary The formation of cummingtonite in two Ca and Al-poor and Mg-rich amphibolites from the Austroalpine Schneeberg complex occurred at a maximum temperature of about 550°C (5 kb). This is a result of the amphibolite facies Alpine overprint in this part of the Eastern Alps.Textural and chemical relations suggest (Mg_–1Si_–1Al₂)-continuous reactions in the bivariant CMASH-assemblageCam-Cum-Chl ^* followed by the discontinuous reactionCam+Chl+Qu=Cum+Plg+H₂O to be responsible for the formation of cummingtonite in these samples.The Mg–Fe distribution coefficient with values of 0.6–0.7 is similar to cummingtonite-Ca-amphibole pairs from amphibolites with oligoclase+quartz reported in the literature. The Mg/(Mg+Fe) ratio of the calcic amphiboles is lower (0.539–0.555) than the coexisting cummingtonites (0.648–0.662).

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Koexistierende Cummingtonite und Hornblenden in Amphiboliten des Schneeberger Zuges, Tirol, Österreich

Zusammenfassung In zwei Ca- und Al-armen Amphiboliten des nördlichen Schneebergerzuges (Rotmoostal) bildete sich Cummingtonit bei Maximaltemperaturen von 550°C (5 kb) bei der Altalpidschen Metamorphose.Texturelle und chemische Beziehungen lassen vermuten, daß sich Cummingtonite sowohl nach kontinuierlichen Reaktionen (in bezug auf den Tschermak-Vektor Mg_–1Si_–1Al₂) gebildet hat, als auch aus Hornblende und Chlorit nach der diskontinuierlichen ACF-ReaktionCam+Chl+Qu=Cum+Plg+H₂O hervorgegangen ist.Der Mg–Fe-Verteilungskoeffizient zwischen Hornblende und Cummingtonit entspricht den aus der Literatur bekannten Werten. Er beträgt zwischen 0.6–0.7 für die beginnende Amphibolitfazies. Die Mg/(Mg+Fe)-Verhältnisse sind höher in Cummingtonit (0.648–0.662) als in der koexistierenden Hornblende (0.539–0.555).

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With 4 Figures     

Orthorhombic amphibole in some metamorphic reactions

The following reactions involving gedrite were experimentally investigated at 500, 1,000 and 2,000 bars H₂O pressure:

1. (1)
   Mg, Fe, Al-chlorite + quartz ? gedrite + cordierite + H₂O and     
   
   

P CO2 in low-grade metamorphism; zeolite,carbonate, clay mineral,prehnite relations in the system CaO-Al2O3-SiO2-CO2-H2O

Equilibria for several reactions in the system CaO-Al₂O₃-SiO₂-CO₂-H₂O have been calculated from the reactions calcite+quartz=wollastonite+CO₂ (5) and calcite+Al₂SiO₅+quartz=anorthite+CO₂ (19) and other published experimental studies of equilibria in the systems Al₂O₃-SiO₂-H₂O and CaO-Al₂O₃-SiO₂-H₂O.The calculations indicate that the reactions laumontite+CO₂=calcite+kaolinite+2 quartz+2H₂O (1) and laumontite+calcite=prehnite+quartz+3H₂O+CO₂ (3) in the system CaO-Al₂O₃-SiO₂-CO₂-H₂O, are in equilibrium with an H₂O-CO₂ fluid phase having -0.0075 for P _fluid=P _total=2000 bars.These calculations limit the stability of zeolite assemblages to low p CO₂.Using the above reactions as model equilibria, several probelms of p CO₂ in low grade metamorphism are discussed. (a) the problem of producing zeolitic minerals from metasedimentary assemblages of carbonate, clay mineral, quartz. (b) the significance of calcite (or aragonite) associated with zeolite (or lawsonite) in low grade metamorphism and hydrothermal alteration. (c) the reaction of zeolites (or lawsonite) with calcite (or aragonite) to produce dense Ca-Al-hydrosilicates (eg. prehnite, zoisite, grossular).     

Jadeite–chloritoid–glaucophane–lawsonite blueschists in north-west Turkey: unusually high P/T ratios in continental crust

Sodic metapelites with jadeite, chloritoid, glaucophane and lawsonite form a coherent regional metamorphic sequence, several tens of square kilometres in size, and over a kilometre thick, in the Orhaneli region of northwest Turkey. The low‐variance mineral assemblage in the sodic metapelites is quartz + phengite + jadeite + glaucophane + chloritoid + lawsonite. The associated metabasites are characterized by sodic amphibole + lawsonite ± garnet paragenesis. The stable coexistence of jadeite + chloritoid + glaucophane + lawsonite, not reported before, indicates metamorphic pressures of 24 ± 3 kbar and temperatures of 430 ± 30 °C for the peak blueschist facies conditions. These P–T conditions correspond to a geotherm of 5 °C km^?1, one of the lowest recorded in continental crustal rocks. The low geotherm, and the known rate of convergence during the Cretaceous subduction suggest low shear stresses at the top of the downgoing continental slab.     

Chloritoid–glaucophane schist in the north Qilian orogen, NW China: phase equilibria and P–T path from garnet zonation

Chloritoid–glaucophane‐bearing rocks are widespread in the high‐pressure belt of the north Qilian orogen, NW China. They are interbedded and cofacial with felsic schists originated from greywackes, mafic garnet blueschists and low‐T eclogites. Two representative chloritoid–glaucophane‐bearing assemblages are chloritoid + glaucophane + garnet + talc + quartz (sample Q5‐49) and chloritoid + glaucophane + garnet + phengite + epidote + quartz (sample Q5‐12). Garnet in sample Q5‐49 is coarse‐, medium‐ and fine‐grained and shows two types of zonation patterns. In pattern I, X_grs is constant as X_py rises, and in pattern II X_grs decreases as X_py rises. Phase equilibrium modelling in the NC(K)MnFMASH system with Thermocalc 3.25 indicates that pattern I can be formed during progressive metamorphism in lawsonite‐stable assemblages, while pattern II zonation can be formed with further heating after lawsonite has been consumed. Garnet growth in Q5‐49 is consistent with a continuous progressive metamorphic process from ～14.5 kbar at 470 °C to ～22.5 kbar at 560 °C. Garnet in sample Q5‐12 develops with pattern I zonation, which is consistent with a progressive metamorphic process from ～21 kbar at 540 °C to ～23.5 kbar at 580 °C with lawsonite present in the whole garnet growth. The latter sample shows the highest P–T conditions of the reported chloritoid–glaucophane‐bearing assemblages. Phase equilibrium calculation in the NCKFMASH system with a recent mixing model of amphibole indicates that chloritoid + glaucophane paragenesis does not have a low‐pressure limit of 18–19 kbar as previously suggested, but has a much larger pressure range from 7–8 to 27–30 kbar, with the low‐pressure part being within the stability field of albite.     

The effect of whole-rock MnO content on the stability of garnet in pelitic schists during metamorphism

Garnet-bearing mineral assemblages are commonly observed in pelitic schists regionally metamorphosed to upper greenschist and amphibolite facies conditions. Modelling of thermodynamic data for minerals in the system Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O, however, predicts that garnet should be observed only in rocks of a narrow range of very high Fe/Mg bulk compositions. Traditionally, the nearly ubiquitous presence of garnet in medium- to high-grade pelitic schists is attributed qualitatively to the stabilizing effect of MnO, based on the observed strong partitioning of MnO into garnet relative to other minerals. In order to quantify the dependence of garnet stability on whole-rock MnO content, we have calculated mineral stabilities for pelitic rocks in the system MnO–Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O for a moderate range of MnO contents from a set of non-linear equations that specify mass balance and chemical equilibrium among minerals and fluid. The model pelitic system includes quartz, muscovite. albite, pyrophyllite, chlorite, chloritoid, biotite, garnet, staurolite, cordierite, andalusite, kyanite. sillimanite, K-feldspar and H₂O fluid. In the MnO-free system, garnet is restricted to high Fe/Mg bulk compositions, and commonly observed mineral assemblages such as garnet–chlorite and garnet–kyanite are not predicted at any pressure and temperature. In bulk compositions with X_Mn= Mn/(Fe + Mg + Mn) > 0.01, however, the predicted garnet-bearing mineral assemblages are the same as the sequence of prograde mineral assemblages typically observed in regional metamorphic terranes. Temperatures predicted for the first appearance of garnet in model pelitic schist are also strongly dependent on whole-rock MnO content. The small MnO contents of normal pelitic schists (X_Mn= 0.01–0.04) are both sufficient and necessary to account for the observed stability of garnet.     

K-rich fluid metasomatism at high-pressure metamorphic conditions: Lawsonite decomposition in rodingitized ultramafite of the Maksyutovo Complex, Southern Urals (Russia)

Fine grained rodingite‐like rocks containing epidote, clinozoisite, garnet, chlorite, phengite and titanite occur within antigorite serpentinite boudins from the high‐pressure metamorphic Maksyutovo Complex in the Southern Urals. Pseudomorphs after lawsonite, resorption of garnet by chlorite and phengite and stoichiometry suggest the reaction lawsonite + garnet + K‐bearing fluid → clinozoisite + chlorite + phengite, and define a relic assemblage of lawsonite + garnet + chlorite + titanite ± epidote as well as a later post‐lawsonite assemblage of clinozoisite + phengite + chlorite + titanite. The reaction lawsonite + titanite → clinozoisite + rutile + pyrophyllite + H₂O delimits the maximum stability of former lawsonite + titanite to pressures >13 kbar. P–T conditions of 18–21 kbar/520–540 °C result, if the average chlorite, Mg‐rich garnet rim and average epidote compositions are used as equilibrium compositions of the former lawsonite assemblage. These estimates indicate a similar depth of formation but lower temperatures to those recorded in nearby eclogites. The metamorphic conditions of the lawsonite assemblage are considerably higher than previously suggested and, together with published structural data, support a model in which a normal fault within the Maksyutovo complex acted as the major transport plane of eclogite exhumation. The maximum Si content of phengite and minimum Fe content in clinozoisite constrain the metamorphic conditions of the later pseudomorph assemblage to be >4.5 kbar and <440 °C. Rb–Sr isotopic dating of the pseudomorph assemblage results in a formation age of 339 ± 6 and 338 ± 5 Ma, respectively. These results support the recent exhumation models for this complex.     

Chemical processes and migration of elements during retrogression of a staurolite-zone assemblage in western North Carolina

A detailed study of retrograde alteration of a staurolite porphyroblast and its surrounding matrix of mica schist has made use of petrographic, modal, and microprobe analysis. Retrogression was to the garnet zone of metamorphism and apparently occurred largely after a temperature decline of 70–100° C. The event caused metasomatic removal of Zn but may have been isochemical relative to other analyzed elements. The best estimate of the overall reaction is: 1 staurolite+3.018 biotite+3.550 quartz+0.629 albite +0.014 anorthite+0.678 NaCl+14.004 H₂O =3.274 Na-rich muscovite+3.561 chlorite +0.273 ilmenite+0.110 chloritoid+0.039 garnet +0.339 ZnCl₂.Non-systematic variation in composition of analyzed minerals is revealed by statistical treatment of replicate analyses. Such variation involves monovalent and divalent cations within many minerals, but is most pronounced within retrograde muscovite. Muscovite variation involves Si and Al as well as FM and alkalis and does not follow a phengite law of charge-coupled substitution.Relative to the core of the retrograded staurolite crystal, zoning is seen in averaged muscovite compositions and in development of incompatible mineral assemblages, which include chloritoid well within retrograded staurolite but biotite within the matrix. A local gradient in the chemical potential of an Al-bearing component was likely present during retrogression.Alteration of staurolite was probably accomplished by reaction and diffusion through the medium of an intergranular fluid phase. Relative to staurolite, migration of elements involved immigration of considerable amounts of Mg, Na, K, and H and expulsion of Al, Fe, Zn, and O. It is inferred that concentration of Al within the fluid phase was considerably lower than those of monovalent and divalent cations.Preservation of considerable staurolite and evidence for a local concentration gradient of Al in the fluid phase suggest that limited amounts of H₂O were available. Expulsion of Zn suggests that much water was not consumed locally but exited the terrane. An attempt at resolution of this dilemna involves fracture-channelized infiltration of H₂O into the rock. A more regional petrographic study of retrogression suggests that H₂O which entered the rock may have been liberated initially by prograde dehydration at a moderately greater depth of 2–3 km.Results of this study, especially the non-phengitic nature of crystal-chemical substitution within muscovite, indicate chemical reaction under conditions of disequilibrium. Apparently, extent of retrogression was controlled by availability of H₂O rather than by thermochemical equilibria.     

Garnet and staurolite producing reactions in a chlorite-chloritoid schist

During prograde metamorphism garnet and, in some higher grade samples, staurolite were produced in a chlorite-chloritoid schist, part of the Precambrian Z to Cambrian Hoosac Formation near Jamaica, VT. Garnet grew during two prograde events separated by a retrogression. This sequence resulted in distinctive inclusion textures and zoning anomalies in garnet produced by diffusive alteration. Textures, reaction space analysis, and mineral compositional variations constrain the possible sequence of reactions in these rocks. Below the staurolite isograd, and to some unknown extent above it, garnet grew by the reaction chloritoid+chlorite+quartz→garnet+H₂O. With increasing grade the mineral compositions are displaced towards lower Mn/Fe and higher Mg/Fe ratios. The data are compatible with equilibrium with respect to exchange reactions for the matrix assemblages on a thin section scale and with minerals having closely followed equilibrium paths during reaction. The staurolite isograd coincides with the reaction chloritoid+quartz→garnet+staurolite+chlorite+H₂O. This reaction is continuous and trivariant with ZnO becoming an additional component concentrated in staurolite. During this reaction both the Mn/Fe and Mg/Fe ratios of the phases appear to have decreased. This new chemical trend is recorded by garnet zoning profiles and is compatible with trends predicted from phase diagrams. Thus there are two distinct types of garnet zoning reversals in these samples. One is near the textural unconformity and is best explained by diffusive alteration during partial resorption of first stage garnet. The other occurs near the outer rim of garnet in staurolite zone samples and marks the onset of a new prograde garnet producing reaction.     

Progressive Low-Grade Metamorphism of a Black Shale Formation, Central Swiss Alps, with Special Reference to Pyrophyllite and Margarite Bearing Assemblages

The unmetamorphosed equivalents of the regionally metamorphosedclays and marls that make up the Alpine Liassic black shaleformation consist of illite, irregular mixed-layer illite/montmorillonite,chlorite, kaolinite, quartz, calcite, and dolomite, with accessoryfeldspars and organic material. At higher grade, in the anchizonalslates, pyrophyllite is present and is thought to have formedat the expense of kaolinite; paragonite and a mixed-layer paragonite/muscovitepresumably formed from the mixed-layer illite/montmorillonite.Anchimetamorphic illite is poorer in Fe and Mg than at the diageneticstage, having lost these elements during the formation of chlorite.Detrital feldspar has disappeared. In epimetamorphic phyllites, chloritoid and margarite appearby the reactions pyrophyllite + chlorite = chloritoid + quartz+ H₂O and pyrophyllite + calcite ± paragonite = margarite+ quartz + H₂O + CO₂, respectively. At the epi-mesozone transition,paragonite and chloritoid seem to become incompatible in thepresence of carbonates and yield the following breakdown products:plagioclase, margarite, clinozoisite (and minor zoisite), andbiotite. The maximum distribution of margarite is at the epizone-mesozoneboundary; at higher metamorphic grade margarite is consumedby a continuous reaction producing plagioclase. Most of the observed assemblages in the anchi-and epizone canbe treated in the two subsystems MgO (or FeO)-Na₂O–CaO–Al₂O₃–(KAl₃O₅–SiO₂–H₂O–CO₂).Chemographic analyses show that the variance of assemblagesdecreases with increasing metamorphic grade. Physical conditions are estimated from calibrated mineral reactionsand other petrographic data. The composition of the fluid phasewas low in X_CO2 throughout the metamorphic profile, whereasX_CH4 was very high, particularly in the anchizone where a_H2Owas probably as low as 0.2. P-T conditions along the metamorphicprofile are 1–2 kb/200–300 °C in the anchizone(Glarus Alps), and 5 kb/500–550 °C at the epi-mesozonetransition (Lukmanier area). Calculated geothermal gradientsdecrease from 50 °C/km in the anchimetamorphic Glarus Alpsto 30 °C/km at the epi-mesozone transition of the Lukmanierarea.     

Mineralogy,petrology, and phase relations of glaucophane-lawsonite zone blueschists from the Tavşanli Region,Northwest Turkey

Glaucophane-lawsonite facies blueschists representing a metamorphosed sequence of basic igneous rocks, cherts and shales have been investigated northeast of the district of Tav?anli in Northwest Turkey. Sodic amphiboles are rich in magnesium reflecting the generally high oxidation states of the blueschists. Lawsonite has a very uniform composition with up to 2.5 wt.% Fe₂O₃. Sodic pyroxenes show an extensive range of compositions with all the end-members represented. Chlorites are uniform in their Al/(Al+Fe+Mg) ratio but show variable Fe/ (Fe+Mg) ratios. Garnets from metacherts are rich in spessartine (>50%) whereas those from metabasites are largely almandine. Pistacite rich epidote is found in metacherts coexisting with lawsonite. Phengites are distinctly higher in their Fe, Mg and Si contents than those from greenschist facies. Hematites with low TiO₂ are ubiquitous in metacherts. Fe²⁺/Mg partitioning between chlorite and sodic amphibole is strongly controlled by the calcium content of the sodic amphibole and ranges from 1.1 for low calcium substitution to 0.8 for higher calcium substitution. The Al/Fe³⁺ partition coefficient between sodic amphibole and sodic pyroxene is 2.1. A model system has been constructed involving projections from lawsonite, iron-oxide and quartz onto a tetrahedron with Na, Al, Fe²⁺ and Mg at its apices. Calcite is treated as an indifferent phase. The model system illustrates the incompatibility of the sodic pyroxene with chlorite in the glaucophanelawsonite facies; this assemblage is represented by sodic amphibole. Sodic amphibole compositions are plotted in terms of coexisting ferromagnesian minerals. Five major areas on the sodic amphibole compositional field are delineated, each associated with one of the following minerals: chlorite, stilpnomelane, talc, almandine, deerite.     

The formation of eclogite facies metatroctolites and a general petrogenetic grid in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O (NCFMASH)

Eclogite facies metatroctolites from a variety of Western Alps localities (Voltri, Monviso, Lanzo, Allalin, Zermat–Saas, etc.) that preserve textural evidence of their original form as bimineralic olivine‐plagioclase rocks are considered in terms of calculated mineral equilibria in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O (NCFMASH). Pseudosections, based on a new petrogenetic grid for NCFMASH presented here, are used to unravel the metamorphic history of the metatroctolites, considering the rocks to consist of different composition microdomains corresponding to the original olivine and plagioclase grains. On the basis that the preservation of the mineral assemblage in each microdomain will tend to be from where on a rock's P–T path the metamorphic fluid phase is used up via rehydration reactions, P–T pseudosections contoured for water content, and P–T path‐M_H2O (amount of water) pseudosections, are used to examine fluid behaviour in each microdomain. We show that the different microdomains are likely to preserve their mineral assemblages from different places on the P–T path. For the olivine microdomain, the diagnostic mineral assemblage is chloritoid + talc (+ garnet + omphacite). The preservation of this assemblage, in the light of the closed system P–T path‐M_H2O relationships, implies that the microdomain loses its metamorphic fluid as it starts to decompress, and, in the absence of subsequent hydration, the high pressure mineral assemblage is then preserved. In the plagioclase microdomain, the diagnostic assemblage is epidote (or zoisite) + kyanite + quartz suggesting a lower pressure (of about 2 GPa) than for the olivine microdomain. In the light of P–T path‐M_H2O relationships, development of this assemblage implies breakdown of lawsonite across the lawsonite breakdown reaction, regardless of the maximum pressure reached. It is likely that the plagioclase microdomain was mainly fluid‐absent prior to lawsonite breakdown, only becoming fluid‐present across the reaction, then immediately becoming fluid‐absent again.